System and method for enhanced recovery of liquid oxygen from a nitrogen and argon producing cryogenic air separation unit

ABSTRACT

A moderate pressure, argon and nitrogen producing cryogenic air separation unit and air separation cycle having a higher pressure column, a lower pressure column and an argon column arrangement is disclosed. The moderate pressure, argon and nitrogen producing cryogenic air separation unit is configured to take a first portion of an oxygen enriched stream from the lower pressure column, which together with an external source of liquid nitrogen is used as the boiling side refrigerant to condense the argon in the argon condenser. Use of the external source of liquid nitrogen in the argon condenser allows a second portion of the oxygen enriched stream from the lower pressure column to be taken as a liquid oxygen product stream.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part application of U.S.patent application Ser. No. 15/962,205 filed Apr. 25, 2018, thedisclosure of which is incorporated by reference herein.

TECHNICAL FIELD

The present invention relates to the enhanced recovery of liquid oxygenfrom a moderate pressure, nitrogen and argon producing cryogenic airseparation unit.

BACKGROUND

Air separation plants targeted for production of nitrogen that operateat moderate pressures (i.e. pressures that are higher than conventionalcryogenic air separation unit pressures) have existed for some time. Inconventional air separation units, if nitrogen at moderate pressure isdesired, the lower pressure column could be operated at a pressure abovethat of conventional air separation units. However, such operation wouldtypically result in a significant decrease in argon recovery as much ofthe argon would be lost in the oxygen rich or nitrogen rich streamsrather than being passed to the argon column.

To increase the argon recovery in such moderate pressure, nitrogenproducing air separation units, a modified air separation cycle wasdeveloped in the late 1980s and early 1990s. See, for example, thetechnical publication Cheung, Moderate Pressure Cryogenic Air SeparationProcess, Gas Separation & Purification, Vol 5, March 1991 and U.S. Pat.No. 4,822,395 (Cheung). In these prior art documents, a nitrogen andargon producing air separation plant with somewhat high argon recoveryis disclosed. The modified air separation cycle involves operating thehigher pressure column at a nominal pressure of preferably between about80 to 150 psia, while the lower pressure column preferably operates at anominal pressure of about 20 to 45 psia, and the argon column would alsopreferably operate at a nominal pressure of about 20 to 45 psia.Recovery of high purity nitrogen (i.e. >99.98% purity) at moderatepressure of about 20 to 45 psia is roughly 94%. High argon recovery at97.3% purity and pressures of between about 20 to 45 psia is generallyabove 90% but is capped at 93%.

In the above described prior art moderate pressure air separationcycles, high purity liquid oxygen from the sump of the lower pressurecolumn is used as the refrigerant in the argon condenser rather thankettle liquid. However, when using the high purity liquid oxygen fromthe sump of the lower pressure column, the argon column needs to operateat higher pressures than conventional argon columns in order to achievethe required temperature difference in the argon condenser. The increasein pressure of the argon column requires the lower pressure column andhigher pressure column to also operate at pressures higher thanconventional air separation units.

The use of high purity liquid oxygen in the argon condenser also meansthat the large kettle vapor stream that normally feeds the lowerpressure column is avoided, which yields a marked improvement inrecovery. As a result, high recoveries of nitrogen, argon, and oxygenare possible with this moderate pressure air separation cycle, eventhough the elevated pressures would otherwise penalize recovery comparedto conventional air separation cycles. The moderate pressure operationof the air separation unit is generally beneficial for nitrogenproduction, as it means the nitrogen compression is less power intensiveand the nitrogen compressor will tend to be less expensive than nitrogencompressors of conventional systems.

Even though the air separation unit in the Cheung publication and U.S.Pat. No. 4,822,395 provides a high purity oxygen vapor exiting the argoncondenser, this oxygen stream is not used as oxygen product because thestream exits the process at too low pressure (e.g. 18 psia) and wouldoften require an oxygen compressor to deliver oxygen product to acustomer at sufficient pressure. In some regions, use of oxygencompressors are generally unacceptable due to safety and costconsiderations. When used, oxygen compressors are very expensive andusually require more complex engineered safety systems, both of whichadversely impacts the capital cost and operating costs of the airseparation unit.

U.S. patent application Ser. Nos. 15/962,205; 15/962,245; and 15/962,297disclose new air separation cycles for moderate pressure cryogenic airseparation units that improve argon recovery and provides for limitedoxygen recovery without the need for oxygen compressors. However, thesenew air separation cycles are operationally limited in applicationsrequiring significant liquid oxygen production make due to the need forrefrigeration duty in the argon condenser and by the added refrigerationpenalty due to higher turbine air stream flow. In addition, any increasein liquid oxygen make beyond a very small amount or rate leads to apenalty in argon recovery and a penalty in nitrogen recovery for cyclesthat employ a lower pressure column turbine cycle.

What is needed are further improved moderate pressure air separationunits and moderate pressure air separation cycles capable of deliveringhigh nitrogen recovery and high argon recovery as well as efficientliquid oxygen production.

SUMMARY OF THE INVENTION

The present invention may be characterized as a nitrogen and argonproducing cryogenic air separation unit comprising: (i) a distillationcolumn system having a higher pressure column and a lower pressurecolumn linked in a heat transfer relationship via a condenser-reboilerand configured to separate an incoming feed air stream and produce anoxygen enriched stream from the base of the lower pressure column and anitrogen product stream from the overhead of the lower pressure column.The distillation column system further includes an argon columnarrangement operatively coupled with the lower pressure column, theargon column arrangement having at least one argon column and an argoncondenser, and wherein the argon column arrangement is configured toreceive an argon-oxygen enriched stream from the lower pressure columnand to produce an oxygen enriched bottoms stream that is returned to orreleased into the lower pressure column and an argon-enriched overheadthat is directed to the argon condenser. The argon condenser isconfigured to condense the argon-enriched overhead against a mixture ofa first portion of the oxygen enriched stream from the lower pressurecolumn and a stream of liquid nitrogen from an external source toproduce a crude argon stream or a product argon stream, an argon refluxstream and an oxygen enriched waste stream while the air separation unitis configured to produce a liquid oxygen product from a second portionof the oxygen enriched stream from the lower pressure column.

Alternatively, the present invention may be characterized as a method ofseparating air in a cryogenic air separation unit to produce one or morenitrogen products, a crude argon product, and a liquid oxygen productcomprising the steps of: (a) separating an incoming feed air stream in adistillation column system having a higher pressure column and a lowerpressure column linked in a heat transfer relationship via acondenser-reboiler to produce an oxygen enriched stream from the base ofthe lower pressure column and a nitrogen product stream from theoverhead of the lower pressure column; (b) further separating anargon-oxygen enriched stream taken from the lower pressure column in anargon column arrangement to produce an oxygen enriched bottoms streamand an argon-enriched overhead; (c) directing the oxygen enrichedbottoms stream into the lower pressure column; (d) directing theargon-enriched overhead to a condensing side of an argon condenser; (e)directing a first portion of the oxygen enriched stream and a stream ofliquid nitrogen from an external source to a boiling side of the argoncondenser; (f) condensing the argon-enriched overhead against the firstportion of the oxygen enriched stream from the lower pressure column andthe liquid nitrogen from an external source to produce a crude argonstream and an argon reflux stream while boiling the first portion of theoxygen enriched stream and the liquid nitrogen to produce an oxygenenriched waste stream; and (g) taking a second portion of the oxygenenriched stream from the lower pressure column as a liquid oxygenproduct.

The higher pressure column is configured to operate at an operatingpressure between 6.0 bar(a) and 10.0 bar(a) and the lower pressurecolumn is configured to operate at an operating pressure between 1.5bar(a) and 2.8 bar(a). Preferably, the argon column is configured tooperate at a pressure of between 1.3 bar(a) and 2.8 bar(a). In normaloperation, the cryogenic air separation has a nitrogen recovery of 98percent or greater of the nitrogen contained in the compressed airstream and an argon recovery of 30 percent or greater.

In most embodiments, the nitrogen and argon producing cryogenic airseparation unit also includes a main air compression system configuredto receive the incoming feed air stream and producing a compressed airstream; an adsorption based pre-purifier unit configured for removingwater vapor, carbon dioxide, nitrous oxide, and hydrocarbons from thecompressed air stream and produce a compressed and purified air stream,wherein the compressed and purified air stream is split into at least afirst part of the compressed and purified air stream and a second partof the compressed and purified air stream; a main heat exchange systemconfigured to cool the first part of the compressed and purified airstream and to partially cool the second part of the compressed andpurified air stream; and a turboexpander arrangement configured toexpand the partially cooled second part of the compressed and purifiedair stream to form an exhaust stream. The distillation column system isconfigured to receive the cooled first part of the compressed andpurified air stream and the exhaust stream and produce one or moreoxygen enriched streams from the base of the lower pressure column and anitrogen product stream from the overhead of the lower pressure column.

In some embodiments, the argon column arrangement includes a superstagedcolumn having between 180 and 260 stages of separation or anultra-superstaged column having between 185 and 270 stages ofseparation. Also, in embodiments where a superstaged argon column isused, a second high ratio argon column may also be used.

The preferred adsorption based pre-purifier unit is a multi-bedtemperature swing adsorption unit configured for purifying thecompressed air stream where each bed alternates between an on-lineoperating phase adsorbing the impurities from the compressed air streamand an off-line operating phase where the bed is being regenerated witha purge gas taken from the oxygen enriched waste stream. Optionally, aregeneration blower may be used to raise the pressure of the purge gas(i.e. oxygen enriched waste stream) by 0.1 bar(a) to 0.3 bar(a).

BRIEF DESCRIPTION OF THE DRAWINGS

While the present invention concludes with claims distinctly pointingout the subject matter that Applicants regard as their invention, it isbelieved that the invention will be better understood when taken inconnection with the accompanying drawings in which:

FIG. 1 is a schematic process flow diagram of an air separation unit inaccordance with an embodiment of the present invention;

FIG. 2 is a schematic process flow diagram of an air separation unit inaccordance with another embodiment of the present invention;

FIG. 3 is a schematic process flow diagram of an air separation unit inaccordance with yet another embodiment of the present invention;

FIG. 4 is a schematic process flow diagram of an air separation unit inaccordance with still another embodiment of the present invention;

FIG. 5 is a schematic process flow diagram of an air separation unit inaccordance with yet another embodiment having increased pressures withindistillation column system;

FIG. 6 is a schematic process flow diagram of an air separation unit inaccordance with yet another embodiment having increased pressures withindistillation column system; and

FIG. 7 is a schematic process flow diagram of an air separation unit inaccordance with still another embodiment of the present invention.

DETAILED DESCRIPTION

The presently disclosed system and method provides for cryogenicseparation of air in a moderate pressure air separation unitcharacterized by a very high recovery of nitrogen, a high recovery ofargon, and limited production of high purity oxygen. As discussed inmore detail below, either a portion of high purity oxygen enrichedstream taken from the lower pressure column or a lower purity oxygenenriched stream taken from the lower pressure column is used as thecondensing medium in the argon condenser to condense the argon-richstream and the oxygen rich boil-off from the argon condenser is thenused as a purge gas to regenerate the adsorbent beds in the adsorptionbased pre-purifier unit. Details of the present system and method areprovided in the paragraphs that follow.

Recovery of Nitrogen, Argon and Oxygen in Moderate Pressure AirSeparation Unit

Turning to the Figs., and in particular FIG. 1, there is shownsimplified schematic illustrations of an air separation unit 10. In abroad sense, the depicted air separation units include a main feed aircompression train or system 20, a turbine air circuit 30, an optionalbooster air circuit 40, a primary heat exchanger system 50, and adistillation column system 70. As used herein, the main feed aircompression train, the turbine air circuit, and the booster air circuit,collectively comprise the ‘warm-end’ air compression circuit. Similarly,main heat exchanger, portions of the turbine based refrigeration circuitand portions of distillation column system are referred to as ‘cold-end’equipment that are typically housed in insulated cold boxes.

In the main feed compression train shown in the Figs., the incoming feedair 22 is typically drawn through an air suction filter house (ASFH) andis compressed in a multi-stage, intercooled main air compressorarrangement 24 to a pressure that can be between about 6.5 bar(a) andabout 11 bar(a). This main air compressor arrangement 24 may includeintegrally geared compressor stages or a direct drive compressor stages,arranged in series or in parallel. The compressed air stream 26 exitingthe main air compressor arrangement 24 is fed to an aftercooler (notshown) with integral demister to remove the free moisture in theincoming feed air stream. The heat of compression from the final stagesof compression for the main air compressor arrangement 24 is removed inaftercoolers by cooling the compressed feed air with cooling towerwater. The condensate from this aftercooler as well as some of theintercoolers in the main air compression arrangement 24 is preferablypiped to a condensate tank and used to supply water to other portions ofthe air separation plant.

The cool, dry compressed air stream 26 is then purified in apre-purification unit 28 to remove high boiling contaminants from thecool, dry compressed air feed. A pre-purification unit 28, as is wellknown in the art, typically contains two beds of alumina and/ormolecular sieve operating in accordance with a temperature swingadsorption cycle in which moisture and other impurities, such as carbondioxide, water vapor and hydrocarbons, are adsorbed. While one of thebeds is used for pre-purification of the cool, dry compressed air feedwhile the other bed is regenerated, preferably with a portion of thewaste nitrogen from the air separation unit. The two beds switch serviceperiodically. Particulates are removed from the compressed, pre-purifiedfeed air in a dust filter disposed downstream of the pre-purificationunit 28 to produce the compressed, purified air stream 29.

The compressed and purified air stream 29 is separated into oxygen-rich,nitrogen-rich, and argon-rich fractions in a plurality of distillationcolumns including a higher pressure column 72, a lower pressure column74, and an argon column 129. Prior to such distillation however, thecompressed and pre-purified air stream 29 is typically split into aplurality of feed air streams, which may include a boiler air stream(See 320 in FIGS. 3 and 4) and a turbine air stream 32. The boiler airstream may be further compressed in a booster compressor arrangement(See 340 in FIGS. 3 and 4) and subsequently cooled in aftercooler (See340 in FIGS. 3 and 4) to form a boosted pressure air stream 360 which isthen further cooled to temperatures required for rectification in themain heat exchanger 52. Cooling or partially cooling of the air streamsin the main heat exchanger 52 is preferably accomplished by way ofindirect heat exchange with the warming streams which include the oxygenstreams 197, 386 as well as nitrogen streams 195 from the distillationcolumn system 70 to produce cooled feed air streams.

The partially cooled feed air stream 38 is expanded in the turbine 35 toproduce exhaust stream 64 that is directed to the lower pressure column74. Refrigeration for the air separation unit 10 is also typicallygenerated by the turbine 35 and other associated cold and/or warmturbine arrangements, such as closed loop warm refrigeration circuitsthat are generally known in the art. The fully cooled air stream 47 aswell as the elevated pressure air stream (See stream 364 in FIGS. 3 and4) are introduced into higher pressure column 72. Optionally, a minorportion of the air flowing in turbine air circuit 30 is not withdrawn inturbine feed stream 38. Optional boosted pressure stream 48 is withdrawnat the cold end of heat exchanger 52, fully or partially condensed, letdown in pressure in valve 49 and fed to higher pressure column 72,several stages from the bottom. Stream 48 is utilized only when themagnitude of pumped oxygen stream 386 is sufficiently high.

The main heat exchanger 52 is preferably a brazed aluminum plate-fintype heat exchanger. Such heat exchangers are advantageous due to theircompact design, high heat transfer rates and their ability to processmultiple streams. They are manufactured as fully brazed and weldedpressure vessels. For small air separation unit units, a heat exchangercomprising a single core may be sufficient. For larger air separationunit units handling higher flows, the heat exchanger may be constructedfrom several cores which must be connected in parallel or series.

The turbine based refrigeration circuits are often referred to as eithera lower column turbine (LCT) arrangement or an upper column turbine(UCT) arrangement which are used to provide refrigeration to atwo-column or three column cryogenic air distillation column systems. Inthe UCT arrangement shown in the Figs., the compressed, cooled turbineair stream 32 is preferably at a pressure in the range from betweenabout 6 bar(a) to about 10.7 bar(a). The compressed, cooled turbine airstream 32 is directed or introduced into main or primary heat exchanger52 in which it is partially cooled to a temperature in a range ofbetween about 140 and about 220 Kelvin to form a partially cooled,compressed turbine air stream 38 that is introduced into a turbine 35 toproduce a cold exhaust stream 64 that is then introduced into the lowerpressure column 74 of the distillation column system 70. Thesupplemental refrigeration created by the expansion of the stream 38 isthus imparted directly to the lower pressure column 72 therebyalleviating some of the cooling duty of the main heat exchanger 52. Insome embodiments, the turbine 35 may be coupled with booster compressor34 that is used to further compress the turbine air stream 32, eitherdirectly or by appropriate gearing.

While the turbine based refrigeration circuit illustrated in the Figs.is shown as an upper column turbine (UCT) circuit where the turbineexhaust stream is directed to the lower pressure column, it iscontemplated that the turbine based refrigeration circuit alternativelymay be a lower column turbine (LCT) circuit or a partial lower column(PLCT) where the expanded exhaust stream is fed to the higher pressurecolumn 72 of the distillation column system 70. Still further, turbinebased refrigeration circuits may be some variant or combination of LCTarrangement, UCT arrangement and/or a warm recycle turbine (WRT)arrangement, generally known to those persons skilled in the art.

The aforementioned components of the incoming feed air stream, namelyoxygen, nitrogen, and argon are separated within the distillation columnsystem 70 that includes a higher pressure column 72, a lower pressurecolumn 74, a super-staged argon column 129, a condenser-reboiler 75 andan argon condenser 78. The higher pressure column 72 typically operatesin the range from between about 6 bar(a) to about 10 bar(a) whereaslower pressure column 74 operates at pressures between about 1.5 bar(a)to about 2.8 bar(a). The higher pressure column 72 and the lowerpressure column 74 are preferably linked in a heat transfer relationshipsuch that all or a portion of the nitrogen-rich vapor column overhead,extracted from proximate the top of higher pressure column 72 as stream73, is condensed within a condenser-reboiler 75 located in the base oflower pressure column 74 against the oxygen-rich liquid column bottoms77 residing in the bottom of the lower pressure column 74. The boilingof oxygen-rich liquid column bottoms 77 initiates the formation of anascending vapor phase within lower pressure column 74. The condensationproduces a liquid nitrogen containing stream 81 that is divided into aclean shelf reflux stream 83 that may be used to reflux the lowerpressure column 74 to initiate the formation of descending liquid phasein such lower pressure column 74 and a nitrogen-rich stream 85 thatrefluxes the higher pressure column 72.

Cooled feed air stream 47 is preferably a vapor air stream slightlyabove its dew point, although it may be at or slightly below its dewpoint, that is fed into the higher pressure column for rectificationresulting from mass transfer between an ascending vapor phase and adescending liquid phase that is initiated by reflux stream 85 occurringwithin a plurality of mass transfer contacting elements, illustrated astrays 71. This produces crude liquid oxygen column bottoms 86, alsoknown as kettle liquid which is taken as stream 88, and thenitrogen-rich column overhead 89, taken as clean shelf liquid stream 83.

In the lower pressure column, the ascending vapor phase includes theboil-off from the condenser-reboiler as well as the exhaust stream 64from the turbine 35 which is subcooled in subcooling unit 99B andintroduced as a vapor stream at an intermediate location of the lowerpressure column 72. The descending liquid is initiated by nitrogenreflux stream 83, which is sent to subcooling unit 99A, where it issubcooled and subsequently expanded in valve 96 prior to introduction tothe lower pressure column 74 at a location proximate the top of thelower pressure column. If needed, a small portion of the subcoolednitrogen reflux stream 83 may be taken via valve 101 as liquid nitrogenproduct 98.

Lower pressure column 74 is also provided with a plurality of masstransfer contacting elements, that can be trays or structured packing orrandom packing or other known elements in the art of cryogenic airseparation. The contacting elements in the lower pressure column 74 areillustrated as structured packing 79. The separation occurring withinlower pressure column 74 produces an oxygen-rich liquid column bottoms77 extracted as an oxygen enriched liquid stream 377 having an oxygenconcentration of greater than 99.5%. The lower pressure column furtherproduces a nitrogen-rich vapor column overhead that is extracted as agaseous nitrogen product stream 95.

Oxygen enriched liquid stream 377 can be separated into a first oxygenenriched liquid stream 380 that is pumped in pump 385 and the resultingpumped oxygen stream 386 is directed to the main heat exchanger 52 whereit is warmed to produce a high purity gaseous oxygen product stream 390.A second portion of the oxygen enriched liquid stream 377 is diverted assecond oxygen enriched liquid stream 90. The second oxygen enrichedliquid stream 90 is preferably pumped via pump 180 then subcooled insubcooling unit 99B via indirect heat exchange with the oxygen enrichedwaste stream 196 and then passed to argon condenser 78 where it is usedto condense the argon-rich stream 126 taken from the overhead 123 of theargon column 129. As an alternative, second oxygen enriched liquidstream 90 may be diverted after pump 385. This will avoid the need forpump 180. As shown in FIG. 1, a portion of the subcooled second oxygenenriched liquid stream 90 may be taken as liquid oxygen product 185.Alternatively, a portion of the first liquid oxygen stream may be takenas liquid oxygen product.

The vaporized oxygen stream that is boiled off from the argon condenser78 is an oxygen enriched waste stream 196 that is warmed withinsubcooler 99B. The warmed oxygen enriched waste stream 197 is directedto the main or primary heat exchanger and then used as a purge gas toregenerate the adsorption based prepurifier unit 28. Additionally, awaste nitrogen stream 93 may be extracted from the lower pressure columnto control the purity of the gaseous nitrogen product stream 95. Thewaste nitrogen stream 93 is preferably combined with the oxygen enrichedwaste stream 196 upstream of subcooler 99B. Also, vapor waste oxygenstream 97 may be needed in some cases when more oxygen is available thanis needed to operate argon condenser 78. This is most likely when argonproduction is reduced.

Liquid stream 130 is withdrawn from argon condenser vessel 120, passedthrough gel trap 370 and returned to the base or near the base of lowerpressure column 74. Gel trap 370 serves to remove carbon dioxide,nitrous oxide, and certain heavy hydrocarbons that might otherwiseaccumulate in the system. Alternatively, a small flow can be withdrawnvia stream 130 as a drain from the system such that gel trap 140 iseliminated (not shown).

Preferably, the argon condenser shown in the Figs. is a downflow argoncondenser. The downflow configuration makes the effective deltatemperature (ΔT) between the condensing stream and the boiling streamsmaller. As indicated above, the smaller ΔT may result in reducedoperating pressures within the argon column, lower pressure column, andhigher pressure column, which translates to a reduction in powerrequired to produce the various product streams as well as improvedargon recovery. The use of the downflow argon condenser also enables apotential reduction in the number of column stages, particularly for theargon column. Use of an argon downflow condenser is also advantageousfrom a capital standpoint, in part, because pump 180 is already requiredin the presently disclosed air separation cycles. Also, since liquidstream 130 already provides a continuous liquid stream exiting the argoncondenser shell which also provides the necessary wetting of thereboiling surfaces to prevent the argon condenser from ‘boiling todryness’.

Nitrogen product stream 95 is passed through subcooling unit 99A tosubcool the nitrogen reflux stream 83 and kettle liquid stream 88 viaindirect heat exchange. As indicated above, the subcooled nitrogenreflux stream 83 is expanded in valve 96 and introduced into anuppermost location of the lower pressure column 74 while the subcooledthe kettle liquid stream 88 is expanded in valve 107 and introduced toan intermediate location of the lower pressure column 74. After passagethrough subcooling units 99A, the warmed nitrogen stream 195 is furtherwarmed within main or primary heat exchanger 52 to produce a warmedgaseous nitrogen product stream 295.

The flow of the first oxygen enriched liquid stream 380 may be up toabout 20% of the total oxygen enriched streams exiting the system. Theargon recovery of this arrangement is between about 75% and 96% which isgreater than the prior art moderate pressure air separation systems. Asdescribed in more detail below with reference to FIG. 7, a stream ofliquid nitrogen taken from an external source may be added to the argoncondenser or may be combined with the second oxygen enriched liquidstream 90 and the combined stream used to condense the argon-rich stream126 in the argon condenser 78, to enhance the argon recovery.

An alternative embodiment of the present air separation unit andassociated air separation cycle is shown in FIG. 2. Many of thecomponents in the air separation plant shown in FIG. 2 are similar tothose described above with reference to FIG. 1 and for sake of brevitywill not be repeated. The differences between the embodiment of FIG. 2compared to the embodiment shown in FIG. 1 is that two separate oxygenenriched liquid streams are taken from the lower pressure column. Thefirst oxygen enriched liquid stream 380 is taken directly from the sumpwhere the oxygen-rich liquid column bottoms 77 are located and hasoxygen concentration of greater than 99.5%. The first oxygen enrichedliquid stream 380 is pumped in pump 385 and directed to the main heatexchanger 52 where it is warmed to produce a high purity gaseous oxygenproduct stream 390. A portion of the first liquid oxygen stream 380 maypreferably be taken as liquid oxygen product 395.

The second oxygen enriched liquid stream 398 is preferably taken fromthe lower pressure column 74 at a location a few stages above the pointwhere the first oxygen enriched liquid stream 380 is extracted and willhave an oxygen concentration between about 94% and 99.7%. The secondoxygen enriched liquid stream 398 is pumped via pump 180 then subcooledin subcooling unit 99B via indirect heat exchange with the oxygenenriched waste stream 196 and then passed to argon condenser 78 where itis used to condense the argon-rich stream 126 taken from the overhead123 of the argon column 129. As with the embodiment of FIG. 1, a streamof liquid nitrogen taken from an external source (not shown) may becombined with the second oxygen enriched liquid stream 398 in an effortto enhance the argon recovery. The combined stream is used to condensethe argon-rich stream 126 in the argon condenser 78.

In FIG. 2, stream 392, after pump 385 is preferably passed through geltrap 370. It is then returned to the base or near the base of lowerpressure column 74. Liquid stream 130 is withdrawn from argon condenservessel 120 and returned to the lower pressure column immediately belowthe draw location of stream 398. Alternatively, a small flow can bewithdrawn via stream 392 as a drain from the system such that gel trap140 is eliminated (not shown). In the case that stream 392 is drainedfrom the system, it can alternatively be diverted from high purityoxygen enriched liquid stream 380, before pump 385. In this case, stream395 can represent a drain stream or a liquid oxygen product stream inaddition to a drain stream

The arrangement shown in FIG. 2 provides four potential advantagescompared to the arrangements of FIG. 1 as well as compared to the priorart systems, particularly for situations where maximum argon recovery isnot needed. The use of the second oxygen enriched liquid stream 398(i.e. lower purity liquid oxygen) instead of the first oxygen enrichedliquid stream 380 does necessarily penalize argon recovery from the airseparation plant since argon is the primary impurity in second oxygenenriched liquid stream 398. A primary benefit of this configuration isthat it enables first oxygen enriched stream 380 to be withdrawn at ahigher oxygen purity.

An additional benefit of the arrangement of FIG. 2 is the capability ofreduced power consumption. Since the lower purity liquid oxygen sent tothe argon condenser boils at a lower temperature, the condensing argonin the argon condenser can be at a lower pressure to achieve therequired delta temperature (ΔT). Lower pressure argon means that theargon column, lower pressure column and higher pressure column canoperate at lower pressures, although the lower pressure column and argoncolumn will still operate at moderate pressures. Because of the lowerpressures in the distillation column system, the power consumption forthe main air compressor system can be reduced.

Another potential benefit of the arrangement shown in FIG. 2 is areduction in the number of separation stages necessary in the argoncolumn due to its lower pressure of operation. A fourth benefit of thearrangement shown in FIG. 2 is that it enables a larger elevatedpressure or pumped oxygen product draw. The reduced argon recoverytranslates to a reduced argon condenser duty, and hence the flow oflower purity oxygen liquid needed for the argon condenser decreases.This, in turn enables a larger pumped oxygen product draw. The pumpedoxygen product may now be as high as 50% of the total oxygen enrichedstreams exiting the system. In this extreme argon recovery may be as lowas 30%.

Yet another alternative embodiment is shown in FIG. 3. Again, since manyof the components in the air separation plant shown in FIG. 3 aresimilar to those described above with reference to FIGS. 1 and 2, thedescriptions of such common components will not be repeated. Thedifference between the embodiment shown in FIG. 3 and the embodiment ofFIG. 1 is the booster air compressor (BAC) circuit.

The BAC circuit shown in FIG. 3 (and FIG. 4) is used to generate anelevated pressure air stream 364 that is higher in pressure than thepumped oxygen stream 386 in the main heat exchanger 52. The BAC circuitpreferably takes a diverted portion of the compressed and purified feedair 29. This diverted BAC stream 320 is then further compressed inbooster air compressor 340 and then cooled in aftercooler 330. Theresulting higher pressure boosted air stream 360 is further cooled inthe main heat exchanger 52 to temperatures suitable for rectification inthe distillation column system 70 while boiling the adjacent pumpedoxygen stream 386 in the main heat exchanger 52. As shown in FIG. 3, theliquefied boosted air stream 364 exiting the cold end of the main heatexchanger 52 is preferably expanded in valve 365 and then supplied tothe higher pressure column 72. The embodiment of FIG. 3 is particularlyuseful when the pumped oxygen stream 386 is of high enough flow orpressure and the BAC circuit is needed to generate an elevated pressureair stream, sufficient in flow and pressure to vaporize the pumpedoxygen stream 386 in the main heat exchanger 52. This arrangement isalso useful to enhance the safety aspects of the air separation unit asthe boosted air stream 360 that is adjacent to the boiling oxygen streamin the main heat exchanger 52 is of higher pressure. The configurationof drain stream 130 and gel trap 370 of FIG. 3 is similar to thatdescribed above with reference to FIG. 1.

Still another alternative embodiment is shown in FIG. 4. Again, sincemany of the components in the air separation plant shown in FIG. 4 aresimilar to those described above with reference to FIG. 3, thedescriptions of such common components will not be repeated. Thedifferences between the embodiment shown in FIG. 4 compared to theembodiment of FIG. 3 is a set of flow control valves 378, 379 thatcontrol the flow of the oxygen enriched liquid stream to the argoncondenser 78.

The embodiment of FIG. 4 is particularly useful for air separation unitsthat require elevated pressures of gaseous oxygen products at both highflow rate and low flow rate. In the embodiment shown in FIG. 4, twovalves are shown to select the source of the oxygen from the lowerpressure column 74 that supplies the argon condenser 78. First valve 378controls the flow of the first oxygen enriched liquid stream 380 takendirectly from the oxygen-rich liquid column bottoms 77 and has oxygenconcentration of greater than 99.5%. Second valve 379 controls the flowof the second oxygen enriched liquid stream 390 having an oxygenconcentration between about 94% and 99.7% that is taken from the lowerpressure column 74 at a location a few stages above the lower pressurecolumn sump or the extraction point of the first oxygen enriched liquidstream 380. The valves 378, 379 preferably work cooperatively in anon/off mode, such that while one valve is open, the other valve isclosed.

If a relatively low gaseous oxygen flow is needed, and higher argonrecovery is desired, the valve 378 is open, and the valve 379 closedsuch that first oxygen enriched liquid stream 380 or higher purityoxygen stream is fed to the argon condenser 78. Conversely, if a highergaseous oxygen flow is needed, or additional power savings is desiredwhen high argon recovery is not needed, valve 378 is closed and valve379 open such that the second oxygen enriched liquid stream 390 or lowerpurity oxygen stream is fed to the boiling side of the argon condenser78. It should be pointed out that the valve 378 is preferably a blockand bleed arrangement to prevent contamination of the oxygen across thevalve 378 in case of leakage.

The resulting oxygen enriched stream 398 is pumped in pump 180 and thensubcooled in subcooling unit 99B via indirect heat exchange with theoxygen enriched waste stream 195 and then passed to the argon condenser78 where it is used to condense the argon-rich stream 126 taken from theoverhead 123 of the argon column 129. As discussed above with referenceto other embodiments, a stream of liquid nitrogen taken from an externalsource (not shown) may be combined with the oxygen enriched liquidstream 398 in an effort to enhance the argon recovery. The combinedstream would be used to condense the argon-rich stream 126 in argoncondenser 78. The configuration of drain streams 130 and 392 and geltrap 370 of FIG. 4 is similar to that described above with reference toFIG. 2.

It should also be pointed out that, in order to be able to achieve thedesired power reduction when the lower purity oxygen is fed to theboiling side of the argon condenser 78, the air separation unit 10 mustbe designed to operate effectively at the lower pressures associatedwith this mode. This means, for example, that the distillation columns72, 74 must be designed for a larger diameter in order to operate atfull capacity when the pressure is lower. Likewise, for the airseparation unit to operate effectively when the higher purity oxygen isfed to the boiling side of the argon condenser 78, the air separationunit 10 must be designed to make the product slate at higher columnpressures. This means that the distillation columns 72, 74 must havesufficient separation stages for this mode, as the relative volatilitiesbetween the components are closer to one another at higher pressures.The main air compressors 24, product compressors (not shown), and boilerair compressor 340 must also be designed to accommodate operation ineither mode. For example, the boiler air compressor 340 may have tooperate with some recirculation circuit 345 when the gaseous oxygenproduct rate is relatively low, unless it is designed with a variablespeed drive or direct drive motor.

Argon Recovery and Refinement

The argon column arrangement employed in the above-described embodimentsmay preferably be configured as: (i) a first argon column (e.g. argonsuperstaged column or crude argon column) operatively coupled with asecond argon column such as a high ratio argon column; or (ii) an argonrejection column or crude argon column integrated with the lowerpressure column structure and preferably coupled to with a downstreamargon refining system.

The embodiment using an argon superstaged column 129 preferably with ahigh ratio argon column 160 is shown in the Figs. The superstaged argoncolumn 129 receives an argon and oxygen containing vapor feed 121 fromthe lower pressure column 74 and down-flowing argon rich reflux 122received from an argon condenser 78 situated above the superstaged argoncolumn 129. The superstaged argon column 129 has between about 180 and260 stages of separation and serves to rectify the argon and oxygencontaining vapor by separating argon from the oxygen into an argonenriched overhead vapor 126 and an oxygen-rich liquid bottoms that isreturned to the lower pressure column as stream 124. The preferred masstransfer contacting elements 125 within the superstaged argon column 129are preferably structured packing. All or a portion of resultingargon-rich vapor overhead 126 is preferably directed to the argoncondenser 78 where it is condensed against the subcooled oxygen enrichedstream from the lower pressure column 74. The resulting condensate is acrude liquid argon stream is taken from the argon condenser 78 most ofwhich is returned to the superstaged argon column 129 as argon refluxstream 127.

The high ratio argon column 160 also receives a portion of the crudeliquid argon stream exiting the argon condenser 78 as stream 162 whichis modulated in pressure in valve 164 and introduced at an intermediatelocation of the high ratio argon column 160. The crude argon isrectified within the high ratio column 160 to form liquid argon bottoms166 and a nitrogen-containing high ratio column overhead 168. A highpurity liquid argon product stream 165 is taken from the liquid argonbottoms 166 of the high ratio argon column 160.

A portion of the nitrogen-rich column overhead extracted from proximatethe top of higher pressure column 72 is also diverted as stream 163 tothe high ratio column reboiler 170 disposed at the bottom of the highratio argon column 160 where the stream is condensed to form liquidnitrogen stream 172. The liquid nitrogen stream 172 is then directed ortransferred to the high ratio column condenser 175 where it provides therefrigeration duty to condense or partially condense the nitrogen-richhigh ratio column overhead 168. The vaporized nitrogen stream 174exiting the high ratio column reboiler 175 is directed to and mixed withthe nitrogen product stream 95 upstream of subcooling unit 99A.

The nitrogen-rich high ratio column overhead 168 is taken from alocation near the top of the high ratio column 160 and subsequentlycondensed or partially condensed in the high ratio column condenser 175.The resulting stream 176 is sent to a phase separator 177 configured tovent the vaporized portion 178 while returning the liquid portion 179 asreflux to the high ratio argon column 160. Using this arrangement, theargon recovery from the air separation plant as high as 96% can beattained.

Other embodiments using alternative argon production and refiningoptions are contemplated for use with the present system and method.Crude argon-rich streams withdrawn from the argon column arrangement canbe recovered or purified in an argon refining system, such as a liquidadsorption based argon purification/refining system, a gaseous phaseadsorption based argon purification/refining system, or a catalyticdeoxo based argon purification/refining system. In another alternative,the high ratio argon column is eliminated, and product purity argon isproduced directly from superstaged column 129 (not shown). In this case,another distillation section is included at the top of the superstagedcolumn. In this section, called a pasteurization zone, small amounts ofnitrogen can be removed to insure reliable product argon purity. Thesmall nitrogen richer stream is vented from the top of column 129 andproduct argon is withdrawn below the pasteurization zone. A tallerdistillation section just above vapor draw stream 121 in lower pressurecolumn is needed so that less nitrogen enters superstaged column 129.This alternative is described in U.S. Pat. No. 5,133,790.

Recovery of Nitrogen and Argon with Increased Pressures in DistillationColumn System

Additional embodiments of the present air separation system and methodare shown in FIG. 5 and FIG. 6. These embodiments allow operation of thehigher pressure column and lower pressure column of the distillationcolumn system at somewhat increased pressures compared to theembodiments described above with reference to FIGS. 1-4, and generallyabove that naturally set by the argon column condenser. Operation of theargon column at minimum pressure, however, is maintained so as to avoida large argon recovery penalty. Argon column minimum pressure is oftenset by the condensation in the argon condenser against low pressureoxygen boiling stream. Increased pressures in the higher pressure columnand lower pressure column of the distillation column system will producea higher pressure gas nitrogen product, although with correspondingdecrease in nitrogen recovery and increase in power consumption. Someadvantages associated with increased pressures of the higher pressurecolumn and lower pressure column may be realized in reduction in cost orpossible elimination of the product nitrogen compressor as well aspossible reduction in column diameters and associated capital costs ofthe lower pressure column and higher pressure column.

The key differences between the embodiment of FIG. 5 and thoseembodiments depicted in FIGS. 1-4 include valve 140 and pump 142. Byletting down the pressure of the argon and oxygen containing vaporstream 121 feeding the argon column, through valve 140, the argon columncan operate at or near its minimum pressure. Because of the lowerpressure of operation of argon column 129 relative to lower pressurecolumn 74, pump 142 is required to return the bottoms liquid 124 fromthe argon column back to the lower pressure column 74. In the embodimentof FIG. 5, the pressure range of the lower pressure column is preferablybetween about 1.7 bar(a) to 3.5 bar(a) while the pressure range of thehigher pressure column is preferably between about 7 bar(a) to 12.5bar(a) and the pressure of the argon column remains between about 1.5bar(a) to about 2.8 bar(a).

In the embodiment of FIG. 6, the argon and oxygen containing vaporstream 121 feeding the argon column first passes into reboiler 143disposed within the base of the argon column 129. The fully condensed orpartially condensed stream 144 is let down in pressure through valve 141and then fed several separation stages above the bottom of the argoncolumn, preferably between about 3 stages and 10 stages above the bottomof the argon column. As a result of the use of reboiler 143, thepressure of lower pressure column 74 must be elevated relative to thepressure of the argon column 129. Specifically, in the embodiment shown,the pressure of the lower pressure column is preferably at least 0.35bar(a) above the pressure in the argon column. While the embodiment ofFIG. 6 includes the additional capital cost associated with the reboiler143 and pump 142, the benefit is that this embodiment should provide anadditional 1% to 5% of argon recovery compared to the embodiment shownin FIG. 5 and should also allow a reduction in the number of separationstages within the argon column.

Enhanced Recovery of Liquid Oxygen Product

An embodiment of the present cryogenic air separation unit andassociated cryogenic air separation cycle that improves the liquidoxygen production is shown in FIG. 2. Many of the components in the airseparation plant shown in FIG. 2 are similar to those described abovewith reference to FIG. 1 and for sake of brevity will not be repeated.The differences between the embodiment of FIG. 2 compared to theembodiment shown in FIG. 1 is the addition of a liquid nitrogen streamfrom an external source of liquid nitrogen or from an integratednitrogen liquefier.

As discussed above, the cryogenic air separation cycles disclosed inU.S. patent application Ser. Nos. 15/962,205; 15/962,245; and 15/962,297are capable of making a small amount of liquid oxygen product. However,the liquid oxygen product make is limited by two factors. First, thecryogenic air separation cycles that employ an upper column turbine(UCT) cycle, requires an increase in the turbine air stream flow to theUCT circuit which may lead to a decrease in nitrogen recovery andgenerally higher power consumption. Second, the cryogenic air separationcycles also require a sufficient supply of refrigeration (via liquidoxygen flow) to the argon condenser. If the liquid oxygen flow to theargon condenser is reduced in order to increase liquid oxygen productextracted from the cryogenic air separation unit results in acorresponding reduction of vapor flow from the lower pressure column tothe argon column. This reduction in vapor flow from the lower pressurecolumn to the argon column yields a proportional reduction in argonrecovery from the air separation unit.

An improved cryogenic air separation cycle that enables higher liquidoxygen product rates without increasing the turbine air stream flow tothe UCT circuit and without reducing vapor flow from the lower pressurecolumn to the argon column is shown in FIG. 7. As seen therein, a streamof liquid nitrogen 500 is added to the cryogenic air separation unit 10to compensate for the increased liquid oxygen make. Unlike theconventional addition of liquid nitrogen to the lower pressure column orthe higher pressure column, the liquid nitrogen stream 500 in FIG. 7 isadded directly to the argon condenser vessel 120 or alternatively may becombined with the liquid oxygen feed stream 190 upstream of the argoncondenser 78.

The addition of liquid nitrogen 500 directly to the argon condenservessel 120 or to the liquid oxygen feed stream 190 upstream of the argoncondenser 78 enables the increase in liquid production with little or nochange in the turbine air stream flow to the UCT circuit. The additionof liquid nitrogen 500 enables the extraction of more liquid oxygenproduct from the cryogenic air separation unit 10 without reducing thecapability of the argon condenser 78 to function at full designcapacity. In this manner, the disclosed cryogenic air separation unit 10and cycle does not penalize nitrogen recovery or argon recovery.

With liquid nitrogen 500 add, the boiling refrigerant in the argoncondenser 78 is a mix of liquid oxygen and liquid nitrogen and will begenerally colder than the boiling refrigerant disclosed in U.S. patentapplication Ser. Nos. 15/962,205; 15/962,245; and Ser. No. 15/962,297.As a result, the distillation column system pressures may be naturallylower than those disclosed in the above-identified United States patentapplication Serial Nos. In other words, the cryogenic air separationunit, and specifically the compressors and distillation column system,may be designed to take advantage of this lower pressure which wouldresult in an overall power savings. Alternatively, if it is notdesirable to design the compressors and distillation columns ofcryogenic air separation unit 10 for the required pressure ranges, thevaporized waste gas 196 from the argon condenser vessel 120 may be backpressured at the warm end of the main heat exchanger 52. By doing thisback pressuring, the boiling fluid temperature in the argon condenser 78is not altered and the distillation column system pressures will alsoremain the same. Employing this alternate back pressuring method wouldbe the likely method of operation of the cryogenic air separation unit10 if the higher liquid oxygen production is expected to be infrequentor non-continuous.

Use of Oxygen Enriched Waste Stream as Regenerating Gas for AdsorptionBased Prepurifier

When using an adsorption based pre-purification unit, it is desirable tohave a continuous flow of compressed, dry, prepurified and cooledstreams of air enter the distillation column system of the airseparation unit. The pre-purification process is preferably done byusing multiple adsorbent beds, preferably arranged as a two-bedtemperature swing adsorption unit. In the preferred two bed temperatureswing adsorption prepurifier, one bed is in an on-line operating phaseadsorbing the impurities in the incoming feed air while the other bed isin an off line operating phase where the bed is being regenerated withall or a portion of the high purity waste oxygen stream. In many two bedadsorption cycles, there may be a short overlap period when both bedsare in an on-line operating phase as the one bed switches from theon-line operating phase to the off-line operating phase and the otherbed switches from the off-line operating phase to the on-line operatingphase.

As is well known in the art, the adsorption bed operating in the on-linephase can only remain on-line until it reaches its capacity to adsorbthe impurities and impurity breakthrough will likely occur. The impuritybreakthrough point is generally defined by the time required for thecontaminants, for instance, water vapor and carbon dioxide, to reachunacceptable levels at the outlet, suggesting the adsorption bed issaturated with contaminants. Once the breakthrough point is approached,the on-line adsorbent bed is brought off-line and the previouslyregenerated bed is brought back on-line to adsorb the impurities in thefeed air.

The preferred temperature swing adsorption unit is a compound adsorbentarrangement that includes at least one layer of alumina 284 below and atleast one layer of molecular sieve 286. Alumina is used to remove mostof the water vapor while the molecular sieve is used to remove watervapor, carbon dioxide, nitrous oxide, and hydrocarbon contaminants fromthe incoming feed air. A compound bed is typically designed with enoughalumina at the bottom of the bed to remove most of the water from thecompressed air feed stream, with the remainder removed by a sieve layerabove it. Compound beds typically have lower purge or regeneration gasflow requirements and require approximately 30% less regeneration energythan all-sieve beds as they can be regenerated at lower temperatures.

Temperature swing adsorption pre-purifiers preferably operate with cycletimes for the “on-line” adsorption in the range of between about 6 and12 hours. Because of these long cycle times, the temperature swingadsorption pre-purifiers can depressurize and re-pressurize over alonger timespan compared to pressure swing adsorption units resulting inmore stable column operation for the air separation unit. Shorter cycletimes help keep initial capital costs low because less adsorbent andshorter adsorbent heights are required in vertical and horizontaloriented beds. However, longer cycle times yield reduced operating costsfrom reduced parasitic losses of blowdown and regeneration energy.Incoming compressed air or feed air temperatures to temperature swingadsorption pre-purifiers can range from 37° F. to as high as 75° F. andtypically the incoming compressed air stream air is preferably cooled tobetween about 40° F. to 60° F. Two common forms of feed air coolers usedto cool the compressed air stream include a dual stage aftercooler and adirect contact aftercooler (not shown).

A temperature swing adsorption prepurifier also requires a purge orregeneration gas flow that is between about 5% and 30% of the feed airor incoming compressed air stream flow, and more preferably a flow equalto about 10% of the incoming compressed air stream. Purge orregeneration gas flow passes through the bed counter-current to the feedair flow. The purge or regeneration gas flow carries regeneration heatinto the bed where it causes the contaminants to desorb from theadsorbent, removes the desorbed contaminants from the bed and cools thebed at the end of the regeneration cycle. At the beginning of theregeneration cycle, the purge gas is heated for the hot purge. Later inthe cycle, the purge gas is not heated, and this is the cold purge.

The regeneration heater must be sized so that it can heat the purge orregeneration gas flow from its initial temperature to the desiredregeneration temperature. Important considerations in regenerationheater sizing are the initial temperature of the purge or regenerationgas, the required purge or regeneration gas flowrate, the heat lossbetween the heater and the adsorbent beds and the heater efficiency.When the regeneration or purge gas is an oxygen enriched stream, theheater outlet temperature should be less than about 400° F. for safetyreasons. With the selection of special materials the heater outlettemperature can be as high as 450° F. safely. In addition, only steam,electric or other non-fired heaters should be used in when theregeneration or purge gas is an oxygen enriched stream.

Regeneration blower 297 is preferably used to raise the pressure ofwaste stream 290 sufficiently to pass through the adsorption basedpre-purification unit for regeneration purposes. Exiting theregeneration blower 297, the pressure of waste stream 290 is raised sothat it will pass through the regeneration heater, prepurifier vesselsand their associated adsorbent beds, and the associated valves to thenvent to the atmosphere. The regeneration blower 297 is preferablyconfigured to raise the pressure of the waste stream 290 exiting themain heat exchanger by about 0.1 bar(a) to 0.3 bar(a).

While us of the regeneration blower is optional, operating the airseparation unit without the regeneration blower requires thedistillation column system to be run at a sufficiently high pressuresuch that that the waste stream exiting main heat exchanger can passthrough the pre-purification unit. Put another way, the use of theregeneration blower allows the reduction in operating pressure of theargon column and the lower pressure column by about 0.15 bar(a) to 0.5bar(a) and reduction in pressure of higher pressure column by about 0.35bar(a) to 2.0 bar(a).

The primary benefit of a regeneration blower in the disclosed airseparation is cycle is primarily related to argon production. Without aregeneration blower, high argon recovery is feasible, but nonethelessthe higher pressure in argon column results in the need for manyseparation stages in the argon column and potentially additional stagesin the lower pressure column. The design and operational sensitivity ofargon recovery is also large. With the use of a regeneration blower, andthe concomitant reduction in distillation column pressures, tends tomake argon recovery more facile. Argon recovery will improve, especiallyin scenarios or embodiments where the targeted argon recovery is lowerand also reduces the staging requirement of argon column and lowerpressure column.

The purge-to-feed (P/F) ratio is the ratio of the purge or regenerationgas flow to the feed air flow. The required P/F ratio is dependent uponseveral variables, including type of adsorbent, regenerationtemperature, cycle time, and hot purge ratio but is preferably in therange of between about 0.05 and 0.40. Higher regeneration temperaturereduces the necessary P/F ratio. Longer cycle times require slightlylower P/F ratios. The hot purge ratio is the ratio of the hot purge timeto the total purge time (i.e. hot purge time plus cold purge time). Ahot purge ratio of about 0.40 is typically used for temperature swingadsorption pre-purifiers to ensure that enough cold purge time isavailable to effectively cool the adsorption bed, but some airseparation units may operate at higher hot purge ratios. Smaller hotpurge ratios result in higher P/F ratios because the same amount of heathas to be carried into the adsorption bed in a shorter amount of time.

Referring back to FIG. 1, a schematic illustration of an air separationunit 10 with a temperature swing adsorption prepurifier 28 is shown. Inthe temperature swing adsorption process there are generally multipledifferent steps that each of the adsorbent beds undergoes, namely:blend; adsorption; blend, depressurization; hot purge; cold purge; andrepressurization. Table 1 below shows the correlation of the performanceof the steps within the two adsorbent beds.

TABLE 1 Example of Two-Bed Temperature Swing Adsorption Cycles and TimesAdsorbent Bed #1 Duration Adsorbent Bed #2 Duration Step # State (min)State (min) 1 Blend 20 Blend 20 2 Depressurization 10 Adsorption 450 3Hot Purge 170 4 Cold Purge 250 5 Repressurization 20 6 Blend 20 Blend 207 Adsorption 450 Depressurization 10 8 Hot Purge 170 9 Cold Purge 250 10Repressurization 20

In the above example, during the “blend” steps, both adsorbent beds are“on-line” and valves 262, 264, 266, and 268 are opened while valves 304,306, 314 and 316 are closed. The feed air stream is split evenly betweenthe two beds during this step with no purge or regeneration gas in thesystem. While “on-line”, adsorbent beds 281 and 282 are adsorbing watervapor and other contaminants such as carbon dioxide. The purpose of thisblend step is to dilute the amount of residual heat left in theadsorbent bed during regeneration and thus prevent a heated stream frombeing fed back to the cold box housing the distillation columns.

Following the “blend” step, one adsorbent, bed 281 is subjected to theregeneration process and is going “off-line” while the other adsorbentbed 282 receives the full feed flow and goes through the adsorption stepwhere water vapor, carbon dioxide, and hydrocarbons continue to beadsorbed. Such regeneration process is completed by way of four distinctsteps including: depressurization; hot purge; cold purge; andrepressurization. It will be appreciated by those skilled in the artthat other steps may also be included. During the depressurization step,adsorption bed 281 depressurizes from the feed pressure to a lowerpressure, typically to near atmospheric pressure. This is accomplishedby closing valves 262 and 266 and opening valve 314. The lower pressureis the regeneration pressure and this step lasts for about 10 minutesbut the length of time can vary depending on equipment constraints orprocess limitations. Once depressurized, the hot purge step starts withthe regeneration oxygen enriched waste stream 290 is heated using theheater 299 to increase the temperature of the oxygen enriched wastestream to a temperature higher than the temperature of the feed air andusually above 300° F. and below 380° F., depending on the process andadsorbent material constraints. Operation as high as 400° F. isallowable. With special material selection the operation can be as highas 450° F. During this time, valve 304 opens and allows the oxygenenriched waste stream to pass through adsorbent bed 281. After a certaintime period elapses, in this example after 170 minutes, the oxygenenriched waste stream by-passes heater 299 or the heater, if an electricheated, is shut-off, lowering the waste stream gas temperature to closeto ambient conditions typically but not always between about 40° F. and100° F. Turning off the electric heater or bypassing the heater startsthe cold purge step, which continues to purge the adsorption bed withthe oxygen enriched waste stream, but without the heat, which lowers thetemperature of the adsorbent bed as well as advancing the heat frontthrough the adsorption bed. In this example this cold purge step lastsabout 250 minutes.

The repressurization step for adsorption bed 281 is initiated by closingvalves 314 and 304 and opening valve 262. This allows part of thecompressed air stream 26 to pressurize the vessel from near ambientpressures to the elevated feed pressure. Once pressurized to the feedpressure, both adsorbent beds 281 and 282 enter the blend step and assuch, valves 266 opens allowing the feed stream to be split evenlybetween adsorbent beds 281 and 282. After a certain amount of time inthe blend step, the beds adsorbent switch and now adsorbent bed 281 ison-line in the adsorption step and adsorbent bed 282 goes through theregeneration steps.

As mentioned above, an air separation process that is conducted inaccordance with the present invention is preferably conducted using thehigher purity oxygen waste stream as the regeneration gas for thetemperature swing adsorption pre-purification unit. Such regeneration ofadsorbent beds using an oxygen stream having a purity greater than 90%has not been used in the prior art air separation plants. The presentinvention, however, allows use of high purity oxygen as the regenerationgas only where the temperature of the regeneration gas is limited to450° F. or more preferably 400° F. which thus allows an overall highernitrogen recovery from the air separation plant. The higher nitrogenrecovery improves the cost efficiency of the nitrogen producing airseparation plant both in terms of lower capital costs and loweroperating costs. For example, the present nitrogen producing airseparation plant sized to produce 3000 mcfh of high purity nitrogen atmoderate pressure and having a 98.0% recovery of nitrogen would require3925 mcfh of feed air that must be compressed, pre-purified, cooled andrectified. On the other hand, the prior art nitrogen producing airseparation plant as described in U.S. Pat. No. 4,822,395 sized toproduce 3000 mcfh of high purity nitrogen at moderate pressure andhaving a 94.6% recovery of nitrogen would require 4066 mcfh of feed airthat must be compressed, pre-purified, cooled, and rectified. Theincreased costs of operating the prior art nitrogen producing airseparation plant may include additional power to compress the increasedvolumetric flow rates of incoming feed air, additional adsorbentmaterials required to pre-purify the higher flows of incoming feed air,and possibly increased capital equipment costs of the turbomachinery,heat exchangers, aftercoolers, pre-purifiers, column internals, etc.that may be required to handle the increased volume of incoming feedair.

It is to be noted here that although water vapor and carbon dioxideremoval is discussed herein, it is understood that other impurities willalso be removed by the adsorbent or adsorbents, for instance nitrousoxide, acetylene and other trace hydrocarbons. However, water vapor andcarbon dioxide are present in much higher concentration than such otherimpurities and will therefore have the greatest impact on the amount ofadsorbent required. Also, while the above discussion is tailored totemperature swing adsorption pre-purifiers, the teachings and scope ofthe invention may also be applicable to some hybrid prepurifierarrangements.

Examples

Tables 2 and 3 below show the results of the computer based processsimulations for the present systems and methods shown and describedabove with reference to FIGS. 1 and 2, respectively. For comparativepurposes, references to the corresponding stream and data from the priorart Cheung system are also included while Table 4 provides thecomparable data from the Cheung prior art system and method. Table 5compares the argon recovery and nitrogen recovery of the selectedembodiments of the present system and compares the recoveries to theargon and nitrogen recovery in the Cheung prior art system. In thesimulation run for the embodiment of FIG. 1, the purity of the oxygenenriched liquid stream is 99.6% and the flow of the pumped liquid oxygenproduct is 2.1% of the total incoming air feed (or 10% of the availableoxygen), while in the simulation run for the embodiment of FIG. 2, thepurity of the second oxygen enriched liquid stream is 94.0% and the flowof the pumped liquid oxygen product is also 2.1% of the total incomingair feed (or 10% of the available oxygen.

TABLE 2 Stream Reference in Ref Cheung Flow Pressure Temp % Oxygen %Nitrogen % Argon  22 (FIG. 1) N/A  100% 14.7 294.3 21.0 78.1 0.9  29(FIG. 1) N/A  100% 120.5 286.0 21.0 78.1 0.9  47 (FIG. 1) Stream 1089.6% 118.3 108.5 21.0 78.1 0.9  36 (FIG. 1) N/A 10.4% 198.1 310.5 21.078.1 0.9  64 (FIG. 1) Stream 23  8.3% 32.9 110.3 21.0 78.1 0.9  90(FIG. 1) 40 28.4% 131.0 98.8 99.6 0.0 0.4 190 (FIG. 1) N/A 28.4% 19.993.2 99.6 0.0 0.4 380 (FIG. 1) Stream 26  2.1% 33.1 98.7 99.6 0.0 0.4390 (FIG. 1) N/A  2.1% 175.0 287.0 99.6 0.0 0.4 196 (FIG. 1) Stream 4118.9% 19.9 93.16 99.5 0.0 0.5 290 (FIG. 1) N/A 18.9% 17.7 287.0 99.5 0.00.5  95 (FIG. 1) Stream 25 77.1% 31.7 84.5 <100 ppb >99.98 <0.02 195(FIG. 1) N/A 78.1% 31.1 103.5 <100 ppb >99.98 <0.02 295 (FIG. 1) N/A78.1% 29.4 287.0 <100 ppb >99.98 <0.02 165 (FIG. 1) Stream 32  0.8% 34.896.3 <1 ppm <1 ppm >99.999 178 (FIG. 1) N/A 0.006%  31.8 88.6 ~100 ppb70.3 29.7 174 (FIG. 1) N/A  1.0% 31.7 85.7 <100 ppb >99.98 <0.02

TABLE 3 Stream Reference in Ref Cheung Flow Pressure Temp % Oxygen %Nitrogen % Argon  22 (FIG. 2) N/A  100% 14.7 294.3 21.0 78.1 0.9  29(FIG. 2) N/A  100% 115.5 286.0 21.0 78.1 0.9  47 (FIG. 2) Stream 1085.0% 113.3 107.3 21.0 78.1 0.9  36 (FIG. 2) N/A 15.0% 188.1 310.5 21.078.1 0.9  64 (FIG. 2) Stream 23  6.5% 31.1 110.2 21.0 78.1 0.9 398 (FIG.2) 40  9.2% 131.0 98.8 93.7 0.0 6.3 190 (FIG. 2) N/A  9.2% 19.9 92.993.7 0.0 6.3 380 (FIG. 2) Stream 26 15.5% 31.4 98.1 99.5 0.0 0.5 390(FIG. 2) N/A  7.3% 175.0 287.0 99.5 0.0 0.5 196 (FIG. 2) Stream 41  6.1%19.9 92.9 93.0 0.0 7.0 290 (FIG. 2) N/A 14.1% 17.7 287.0 96.6 0.0 3.4 95 (FIG. 2) Stream 25 77.9% 29.8 83.9 <100 ppb >99.9 <0.1 195 (FIG. 2)N/A 78.1% 29.4 96.2 <100 ppb >99.9 <0.1 295 (FIG. 2) N/A 78.1% 29.4287.0 <100 ppb >99.9 <0.1 165 (FIG. 2) Stream 32  0.3% 33.2 95.7 <1 ppm<1 ppm >99.999 178 (FIG. 2) N/A 0.002%  30.2 88.0 ~100 ppb 70.7 29.3 174(FIG. 2) N/A  0.3% 29.8 85.8 <100 ppb >99.9 <0.01

TABLE 4 Stream Reference in Ref Present FIGS. Flow Pressure Temp %Oxygen % Nitrogen % Argon 10 (Cheung) 41 (FIGS. 1 & 2) (92.7%) 117.9 109.3  21.0 78.1 0.9 23 (Cheung) 64 (FIGS. 1 & 2) (7.3%) 30.4 95.3 21.078.1 0.9 25 (Cheung) 95 (FIGS. 1 & 2) 73.9% 27.7 83.2 1 ppm >99.98 — 40(Cheung) 398 (FIGS. 1 & 2) — — — ≥99.75 0 — 26 (Cheung) 380 (FIGS. 1 &2) — — — — 0 ≥0.25  41 (Cheung) 196 (FIGS. 1 & 2) — — — ≥99.75 0 — 42(Cheung) 196 + 380 (FIGS. 1/2) 21.0% 18.2 92.6 99.75 0  0.25 32 (Cheung)165 (FIGS. 1/2) 0.9% 27.3 93.6 1.9 0.8 97.3 

TABLE 5 Air Separation System Argon Recovery Nitrogen Recovery Cheung(Prior Art) 92.7% 94.6%/91.6% Present System (FIG. 1) ≥88.6%* 99.99%Present System (FIG. 2) ≥30.6%** 99.99% *Depending on volume of highpurity pumped liquid oxygen product taken (i.e. stream 386) **Dependingon volume of high purity pumped liquid oxygen product taken (i.e. stream386) and oxygen purity of second oxygen enriched liquid stream (i.e.stream 398)

Gas recoveries disclosed in U.S. Pat. No. 4,822,395 (Cheung) and shownin Table 5 above, represent cold box recoveries and do not account forpotential losses in the main heat exchanger or in regeneration of theprepurifier beds. Table 5 provides both the disclosed argon recovery inCheung from the cold box (92.7%) and the estimated argon recovery fromthe entire air separation unit (92.7%) Likewise, Table 5 also providesboth the disclosed nitrogen recovery in Cheung from the cold box (94.6%)and the estimated nitrogen recovery from the entire air separation unit(91.6%). Such estimates are based on a technical paper authored byCheung as well as actual embodiments of the Cheung plant installed inthe field. The estimated nitrogen recovery in Cheung represents theremaining nitrogen available as a nitrogen product after blending someof the nitrogen with the waste stream to bring the oxygen purity in thewaste stream down to 80% (i.e. prior art levels of oxygen inregeneration of adsorption based prepurifier units for air separationplants).

Although the present system for recovery of argon and nitrogen from anair separation unit has been discussed with reference to one or morepreferred embodiments and methods associated therewith, as would occurto those skilled in the art that numerous changes and omissions can bemade without departing from the spirit and scope of the presentinventions as set forth in the appended claims.

What is claimed is:
 1. A nitrogen and argon producing cryogenic airseparation unit comprising: a distillation column system having a higherpressure column and a lower pressure column linked in a heat transferrelationship via a condenser-reboiler and configured to separate anincoming feed air stream and produce an oxygen enriched stream from thebase of the lower pressure column and a nitrogen product stream from theoverhead of the lower pressure column; the distillation column systemfurther includes an argon column arrangement operatively coupled withthe lower pressure column, the argon column arrangement having at leastone argon column and an argon condenser, and wherein the argon columnarrangement is configured to receive an argon-oxygen enriched streamfrom the lower pressure column and to produce an oxygen enriched bottomsstream that is returned to or released into the lower pressure columnand an argon-enriched overhead that is directed to the argon condenser;wherein the argon condenser is configured to condense the argon-enrichedoverhead against a mixture of a first portion of the oxygen enrichedstream from the lower pressure column and a stream of liquid nitrogenfrom an external source to produce a crude argon stream or a productargon stream, an argon reflux stream and an oxygen enriched wastestream; and wherein the air separation unit is configured to produce aliquid oxygen product from a second portion of the oxygen enrichedstream from the lower pressure column.
 2. The nitrogen and argonproducing cryogenic air separation unit of claim 1, further comprising:a main air compression system configured to receive the incoming feedair stream and producing a compressed air stream; an adsorption basedpre-purifier unit configured for removing water vapor, carbon dioxide,nitrous oxide, and hydrocarbons from the compressed air stream andproduce a compressed and purified air stream, wherein the compressed andpurified air stream is split into at least a first part of thecompressed and purified air stream and a second part of the compressedand purified air stream; a main heat exchange system configured to coolthe first part of the compressed and purified air stream and topartially cool the second part of the compressed and purified airstream; and a turboexpander arrangement configured to expand thepartially cooled second part of the compressed and purified air streamto form an exhaust stream; wherein the distillation column system isconfigured to receive the cooled first part of the compressed andpurified air stream and the exhaust stream and produce one or moreoxygen enriched streams from the base of the lower pressure column and anitrogen product stream from the overhead of the lower pressure column.3. The nitrogen and argon producing cryogenic air separation unit ofclaim 1, wherein the higher pressure column is configured to operate atan operating pressure between about 6.0 bar(a) and 10.0 bar(a) and thelower pressure column is configured to operate at an operating pressurebetween about 1.5 bar(a) and 2.8 bar(a).
 4. The nitrogen and argonproducing cryogenic air separation unit of claim 1, wherein thecryogenic air separation unit has a nitrogen recovery of 98 percent orgreater of the nitrogen contained in the compressed air stream and anargon recovery of 30 percent or greater of the argon contained in thecompressed air stream.
 5. The nitrogen and argon producing cryogenic airseparation unit of claim 1, wherein the volumetric flow rate of thestream of liquid nitrogen from the external source is less than or equalto the volumetric flow rate of the stream of liquid oxygen product takenfrom the cryogenic air separation unit.
 6. The nitrogen and argonproducing cryogenic air separation unit of claim 1, wherein thevolumetric flow rate of the first portion of the oxygen enriched streamfrom the lower pressure column to the argon condenser is greater thanthe volumetric flow rate of the liquid nitrogen from the external sourceto the argon condenser.
 7. The nitrogen and argon producing cryogenicair separation unit of claim 4, wherein the adsorption basedpre-purifier unit is a multi-bed temperature swing adsorption unitconfigured for purifying the compressed air stream, the multi-bedtemperature swing adsorption unit is further configured such that eachbed alternates between an on-line operating phase adsorbing the watervapor, carbon dioxide, nitrous oxide, and hydrocarbons from thecompressed air stream and an off-line operating phase where the bed isbeing regenerated with a purge gas taken from the oxygen enriched wastestream.
 8. The air separation unit of claim 7, further comprising aregeneration blower configured to raise the pressure of the oxygenenriched waste stream by about 0.1 bar(a) to 0.3 bar(a).
 9. The nitrogenand argon producing cryogenic air separation unit of claim 1, whereinthe argon column is configured to operate at a pressure of between about1.3 bar(a) and 2.8 bar(a).
 10. The nitrogen and argon producingcryogenic air separation unit of claim 9, wherein the argon column inthe argon column arrangement is a superstaged column having between 180and 260 stages of separation or an ultra-superstaged column havingbetween 185 and 270 stages of separation.
 11. The nitrogen and argonproducing cryogenic air separation unit of claim 9 wherein the argoncolumn arrangement further comprises a first argon column configured asa superstaged argon column, a second argon column configured as a highratio argon column.
 12. A method of separating air in a cryogenic airseparation unit to produce one or more nitrogen products, a crude argonproduct, and a liquid oxygen product comprising the steps of: (a)separating an incoming feed air stream in a distillation column systemhaving a higher pressure column and a lower pressure column linked in aheat transfer relationship via a condenser-reboiler to produce an oxygenenriched stream from the base of the lower pressure column and anitrogen product stream from the overhead of the lower pressure column;(b) further separating an argon-oxygen enriched stream taken from thelower pressure column in an argon column arrangement to produce anoxygen enriched bottoms stream and an argon-enriched overhead; (c)directing the oxygen enriched bottoms stream into the lower pressurecolumn; (d) directing the argon-enriched overhead to a condensing sideof an argon condenser; (e) directing a first portion of the oxygenenriched stream from the lower pressure column and a stream of liquidnitrogen from an external source to a boiling side of the argoncondenser; (f) condensing the argon-enriched overhead against the firstportion of the oxygen enriched stream from the lower pressure column andthe liquid nitrogen from an external source to produce a crude argonstream and an argon reflux stream while boiling the first portion of theoxygen enriched stream and the liquid nitrogen to produce an oxygenenriched waste stream; and (g) taking a second portion of the oxygenenriched stream from the lower pressure column as a liquid oxygenproduct; wherein the cryogenic air separation unit produces the one ormore nitrogen products with a total nitrogen recovery of 98 percent orgreater of the nitrogen contained in the incoming feed air stream andproduces the crude argon with an argon recovery of 30 percent or greaterof the argon contained in the incoming feed air stream.
 13. The methodof claim 12, wherein the volumetric flow rate of the stream of liquidnitrogen directed to from the external source is less than or equal tothe volumetric flow rate of the stream of liquid oxygen product taken.14. The method of claim 12, wherein the volumetric flow rate of thefirst portion of the oxygen enriched stream from the lower pressurecolumn directed to the argon condenser is greater than the volumetricflow rate of the liquid nitrogen from the external source directed tothe argon condenser.
 15. The method of claim 12, further comprising thesteps of: (a1) compressing the incoming feed air stream to produce acompressed air stream; (a2) purifying the compressed air stream in anadsorption based pre-purifier unit configured for removing water vapor,carbon dioxide, nitrous oxide, and hydrocarbons from the compressed airstream to produce a compressed and purified air stream; (a3) splittingthe compressed and purified air stream into at least a first part of thecompressed and purified air stream and a second part of the compressedand purified air stream; (a4) cooling the first part of the compressedand purified air stream and the second part of the compressed andpurified air stream in a main heat exchanger system; (a5) expanding thecooled second part of the compressed and purified air stream in aturboexpander arrangement to form an exhaust stream; (a6) directing theexhaust stream and the cooled first part of the compressed and purifiedair stream to the distillation column system; and (a7) separating theexhaust stream and the cooled first part of the compressed and purifiedair stream in the distillation column system to produce the oxygenenriched stream from the base of the lower pressure column and thenitrogen product stream from the overhead of the lower pressure column.16. The method of claim 15, wherein the higher pressure column isconfigured to operate at an operating pressure between about 6.0 bar(a)and 10.0 bar(a) and the lower pressure column is configured to operateat an operating pressure between about 1.5 bar(a) and 2.8 bar(a). 17.The method of claim 15, wherein the adsorption based pre-purifier unitis a multi-bed temperature swing adsorption unit configured forpurifying the compressed air stream, and wherein the multi-bedtemperature swing adsorption unit is further configured such that eachbed alternates between an on-line operating phase adsorbing the watervapor, carbon dioxide, nitrous oxide, and hydrocarbons from thecompressed air stream and an off-line operating phase where the bed isbeing regenerated with a purge gas taken from the oxygen enriched wastestream.
 18. The method of claim 17 wherein the pressure of the oxygenenriched waste stream is raised by about 0.1 bar(a) to 0.3 bar(a) usinga regenerator blower.
 19. The method of claim 12, wherein the argoncolumn is configured to operate at a pressure of between about 1.3bar(a) and 2.8 bar(a).
 20. The method of claim 12, wherein the argoncolumn arrangement further comprises a superstaged argon column havingbetween 180 and 260 stages of separation or an ultra-superstaged columnhaving between 185 and 270 stages of separation.